Anna Orlikowska

Dioxin-like compounds in pine needles around Tokyo Bay, Japan in 1999.

Pine needle samples collected at ten spatially distant sites around Tokyo Bay in 1999 indicated a widespread lower troposphere pollution with ultra-trace dioxin-like compounds such as chlorodibenzo-p-dioxins (PCDDs), -furans (PCDFs), non-ortho- and mono-ortho-chlorobiphenyls (pPCBs), and -naphthalenes (PCNs). Elevated concentration of planar PCBs and the total PCNs were found at the sites which are located innermost to the Bay, suggesting the regional importance of the evaporative nature of the source of pollution by those compounds over this vast area. The concentrations and profiles for PCDDs and PCDFs remained largely uniform. An exception was the site near the town of Tateyama in the Chiba Prefecture, which is the southernmost but also relatively separate from the inner Bay. The site near Tateyama showed somehow background contamination with all compound groups and highly different profiles of PCNs. The principal component analysis (PCA) of the data matrix has revealed that around the Tokyo Bay, apart from the evaporative emission sources for PCNs and PCBs, combustion related processes also play an important role as sources of the ambient air contamination not only with PCDDs/Fs but also with chloronaphthalenes and planar chlorobiphenyls.

Some Chemical Contaminant of Surface Sediments at the Baltic Sea Coastal Region with Special Emphasis on Androgenic and Anti-Androgenic Compounds

Androgenic and anti-androgenic compounds including p,p′-DDE, Diuron, Linuron, Fenarimol, Vinclozolin, 1-(3,4-dichlorophenyl) urea (DCPU), 1-(3,4-dichlorophenyl)-3-methylurea, (DCPMU), tributyltin (TBT) and triphenyltin (TPT) and their metabolites (DBT, MBT, DPT, MPT) as well as metallic elements (Ni, Cu, Zn, As, Cd, Pb, Co, Tl, Cr, Fe, Mn, Al, K, Mg, Na, Ca, Ba, Ti, Sn), PAHs (16 indicator compounds), DDTs and PCBs have been quantified in top layer (0–10 cm) of up to 37 surface sediment samples collected from several sites in costal zone of the Gulf of Gdańsk, an inland freshwater area of Brdyujście in Poland and the tidal flats of the Norderney Island, Wadden Sea in 2002–2003. These sites differed in the degree of anthropogenic activities, including chemical pollution and related impact on biota. Especially in sediments near shipyards, ship repair facilities, harbours, other industrial activities or close to municipal sewage treatment plant outlets butyltins, PAHs and some metallic elements were found at high concentrations. Diuron, Linuron and DCPMU were detected at a few sites, Fenarimol only once, while Vinclozolin and DCPU were not detected. DDT concentrations in the sediments from the Gdańsk and Gdynia region of the Gulf show a stepwise decrease following the ban for production and use, while diffusion of PCBs at some industrial sites seems to continue. Elevated PAH concentrations in sediments seem to be mainly due to pyrogenic and less to mixed pyrogenic and petrogenic sources, while for a few sites rather petrogenic sources dominated. The reference sites in the Norderney Island, Wadden Sea showed similar or slightly higher loads of DDTs, BTs, PAHs, PCBs and metallic elements when compared to sediments from the least contaminated sites in the coastal Gulf of Gdańsk area, while phenyltins were not detected at both spatially distant European areas.

Airborne chloronaphthalenes in Scots pine needles of Poland

The amounts, profiles and origin of CNs (from triCNs to octaCN) sequestered in Scots pine needles collected from 25 spatially distant sites in Poland have been studied based on congener-specific data obtained after a several clean-up and fractionation steps and final HRGC/HRMS separation and determination. The absolute concentrations of CNs varied largely from site to site, i.e., by 15-fold. The sum of tri- to octaCN concentration at fifteen of the least contaminated sites ranged from 70 to 280 pg g(-1) ww, and at further eight sites were from 340 to 540 pg g(-1) ww, while at two the most contaminated were 1000 and 1100 pg g(-1)ww. There were some substantial similarities but also variations in triCN to octaCN homologue group profiles depending on the site. Among triCNs the isomers such as 1,2,4-/1,3,7-/1,4,6-triCNs (nos. 14/21/24) dominate in Scots pine needles. For majority of the sites examined 1,2,4-/1,3,7-/1,4,6-triCNs are also the major contributors to the bulk of CNs determined. Among tetraCNs isomer 1,2,5,8-tetraCN (no. 38) was dominant contributor at eighteen sites, while 1,2,4,6-/1,2,4,7-/1,2,5,7-tetraCN (nos. 33/34/37) at seven other sites. In the case of pentaCNs isomer 1,2,4,5,8-pentaCN (no. 59), was dominant contributor alone. Octachloronaphthalene frequently contributed substantially to the bulk of CNs. The Cluster Analysis and Principal Component Analysis did indicate that the compositional profiles of CNs found in Scots pine needles resemble somehow these found in the bottom ashes after coke and coal burning as well as of Halowax 1000 and 1099 formulations.

Dioxin-like compound compositional profiles of furnace bottom ashes from household combustion in Poland and their possible associations with contamination status of agricultural soil and pine needles.

A compositional profile of PCDDs, PCDFs, non- and mono-ortho PCBs, and PCNs of several type furnace bottom ashes obtained after the heating muffle stove for domestic use combustion of hard coal, coke, wood, and solid domestic waste mixture have been examined as possible contributors to environmental diffusion with these compounds in Poland. The uppermost concentration of dioxin-like compounds with 2.0 ng TEQ kg(-1) dry weight found for wood ash was dominated by PCDDs and PCDFs, while for other types of ashes were in the range from 0.052 ng TEQ kg(-1) to 0.67 ng TEQ kg(-1) dry weight. The multivariate statistical analysis displayed some compositional similarity of PCDDs, PCDFs and PCNs between the ashes and environmental pine needle or agricultural soil matrices collected in Poland.

Polychlorinated dibenzo-p-dioxins (PCDDs) and -furans (PCDFs) in pine needles of Poland.

There is scarcity of data on sources, environmental diffusion and concentrations of PCDD/Fs and dioxin-like compounds in the Eastern and Central Europe. A study has been conducted using pine needles as passive matrix on diffusion of airborne 17 highly toxic PCDD/Fs in Poland. The target compounds were quantified using isotope dilution and HRGC/HRMS. One-year-old pine needles collected from 25 spatially distant sites in October 2002 revealed a relatively very low aerial emission and degree of pollution with PCDD/Fs. The most toxic 2,3,7,8-TCDD was absent (< 0.44 pg/g) in fresh pine needles sampled and absent at all sites were also 1,2,3,7,8-PeCDD, 1,2,3,4,7,8-HxCDD, 1,2,3,6,7,8-HxCDD, 1,2,3,7,8,9-HxCDD and 1,2,3,7,8,9-HxCDF (< 0.27 pg/g). OCDD at concentration range from 1.4 to 34 pg/g and OCDF at range from 1.5 to 41 pg/g were the only among 17 compounds found at each site, and next in prevalence was 1,2,3,4,7,8,9-HpCDF (total range from < 0.41 to 8.1 pg/g), which was found at 24 off 25 sites. The I-TEQ transformed concentrations of PCDD/Fs of pine needles of Poland ranged from < 0.01 to 1.28 pg/g ww or from 0.01 to 3.18 pg/g dw. The CDD/F homologue groups and congeners profiles of pine needles with highly dominant HpCDD/F and OCDD/F found in this survey suggest on lack of significant other than coal/lignite/wood combustiont sources of PCDD/Fs diffusion to ambient air in Poland.

Levels and sources of planar and non-planar PCBs in pine needles across Poland

Under a small project, one-year-old Scots Pine needles collected from 25 spatially distant sites were examined in monitoring the extent of environmental diffusion and possible sources of polychlorinated biphenyls (PCBs) in ambient air, their depositions and uptake by plants in Poland. The congener-specific determination of planar and non-planar chlorobiphenyls was achieved by isotope dilution HRGC-HRMS method after a highly refined extraction on multi-layer column of silica gel and alumina layer and clean-up, and fractionations, followed by Hypercarb-HPLC and PYE-HPLC sub-fractionation steps. Contents of 117 chlorobiphenyls determined in pine needles varied for the 25 sites studied and is between 2.7 and 49 ng/g wet weight. The PCBs pollution and congener-specific composition of pine needles to some degree varied according to the site or region surveyed depending on population density and industrialization. Many of the country-side areas showed lower concentrations between 2.7 and 8.9 ng/g ww. Pine needles in areas close to well populated and industrial regions of Opole, Kutno, Włocławek and Dębica showed the highest PCB pollution with concentrations varying between 30 and 49 ng/g ww. The Kutno site showed the highest pollution and this fact probably can be explained by possible emission from transformer manufactures located at some distance west of the Kutno area. Factor analysis (FA) and depending on the site revealed on relationship of PCBs composition of pine needles both with highly chlorinated PCB constituents of the mixtures such as Chlorofen, Aroclor 1254, Aroclor 1268 and Sovol but also of lower chlorinated PCB constituents of Aroclor 1242, Aroclor 1248, Clophen A40 or Delor 103. Thermal processes were considered a less significant source of PCBs in ambient air over Poland compared to evaporative sources related to technical PCB formulations. Supplemental materials are available for this article. Go to the publishers online edition of Journal of Environmental Science and Health: Part A to view the free supplemental file.

By-side PCDD/Fs in technical PCB formulations of Kanechlor series

The Japanese Kanechlor technical PCB formulations such as KC-300, KC-400, KC-500, KC-600 and KC-1000 have been examined for possible contamination with by-side PCDD/Fs. 75 PCDDs and 135 PCDF have been determined using isotope dilution, separation and enrichment on silica gel impregnated with activated carbon, and final HRGC/HRMS measurement. MonoCDDs to OCDD were absent in KC-300, KC-600 and KC-1000. Tetra- and PentaCDDs occurred at > 1 ng/g in KC-400 and KC-500. The Kanechlors were contaminated with nearly all 135 PCDFsw. In parallel with an increasing degree of chlorination of a particular Kanechlor formulation examined increased also the content of more chlorinated PCDFs. In term of total dioxin-like toxicity and TEQ loads the KC-500 contained highly toxic PCDD/Fs at 270 ng TEQ/g and followed by KC-400 with 269 ng TEQ/g, KC-600 with 188 ng TEQ/g, KC-1000 with 164 ng TEQ/g and KC-300 with 79 ng TEQ/g. From 99.5 to 100% of PCDD/Fs toxicity found in the Kanechlors was from PCDFs.